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US20160152787A1 - Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin - Google Patents

Blowing agent composition of hydrochlorofluoroolefin and hydrofluoroolefin Download PDF

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Publication number
US20160152787A1
US20160152787A1 US15/015,184 US201615015184A US2016152787A1 US 20160152787 A1 US20160152787 A1 US 20160152787A1 US 201615015184 A US201615015184 A US 201615015184A US 2016152787 A1 US2016152787 A1 US 2016152787A1
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Prior art keywords
hfo
blowing agent
hcfo
isomers
hydrofluoroolefin
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Granted
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US15/015,184
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US9914815B2 (en
Inventor
Benjamin Bin Chen
Joseph S. Costa
Philippe Bonnet
Maher Y. Elsheikh
Brett L. Van Horn
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Arkema Inc
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Arkema Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • B01F17/0085—
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017—Mixtures of compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2300/104—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2300/106—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to blowing agents for thermosetting foams. More particularly, the present invention relates to the use of at least one hydrofluoroolefin such as HFO-1234yf in combination with at least one hydrochlorofluoroolefin (HCFO) such as HCFO-1223, HCFO-1233zd, HCFO-1233xf and mixtures thereof as a blowing agent in the manufacture of thermosetting foams.
  • HFO hydrofluoroolefin
  • HCFO hydrochlorofluoroolefin
  • thermoset foams include HFC-134a, HFC-245fa, HFC-365mfc that have relatively high global warming potential, and hydrocarbons such as pentane isomers flammable and have low energy efficiency. Therefore, new alternative blowing agents are being sought.
  • Halogenated hydroolefinic materials such as hydrofluoropropenes and/or hydrochlorofluoropropenes have generated interest as replacements for HFCs. The inherent chemical instability of these materials in the lower atmosphere provides the low global warning potential and zero or near zero ozone depletion properties desired.
  • the object of the present invention is to provide novel compositions that can serve as blowing agents for thermosetting foams that provide unique characteristics to meet the demands of low or zero ozone depletion potential, lower global warming potential and exhibit low toxicity.
  • the present invention relates to the use of blowing agents with negligible (low or zero) ozone-depletion and low global warming potential based upon unsaturated halogenated hydroolefins.
  • the blowing agents comprise at least one hydrofluoroolefin preferably (HFO) HFO-1234yf in a combination with at least one hydrochlorofluoroolefin (HCFO) such as HCFO-1223, HCFO-1233zd, HCFO-1233xf and mixtures thereof.
  • HFO-1234yf is 2,3,3,3-tetrafluoropropene; HCFO 1223 is dichlorotrifluoropropene; HCFO-1233zd is 1-chloro-3,3,3-trifluoropropene; HCFO1233xf is 2-chloro-3,3,3-trifluoropropene.
  • the composition can further comprise an additional hydrofluoroolefin (HFO), a hydrofluorocarbon, a hydrocarbon, an alcohol, an ester, an aldehyde, a ketone ether/diether, carbon dioxide and mixtures thereof.
  • HFO hydrofluoroolefin
  • Hydrofluoroolefin (HFO) materials have been proposed as blowing agents which exhibit a low global warming potential and a low ozone depletion value.
  • the low global warming potential and a low ozone depletion value are a result of the atmospheric degradation of the hydrofluoroolefins.
  • the hydrofluoroolefin preferably HFO-1234yf in combination with a hydrochlorofluoroolefin (HCFO) preferably selected from HCFO-1223, HCFO-1233zd, HCFO-1233xf and mixtures thereof combination can be used as a foaming agent for thermosetting foams by being mixed in a polyols mixture.
  • HCFO hydrochlorofluoroolefin
  • the resulted products show superior quality including decreased density and improved k-factor.
  • the foaming agent dissolves in thermosetting polymers, and provides a degree of plasticization sufficient to produce acceptable foams.
  • the preferred blowing agent composition hydrofluoroolefin, preferably HFO-1234yf in combination with a hydrochlorofluoroolefin (HCFO) preferably selected from HCFO-1223, HCFO-1233zd, HCFO-1233xf and mixtures thereof of the present invention exhibits good solubility in polyol mixture used in producing polyurethane and polyisocyanurate foams.
  • HCFO hydrochlorofluoroolefin
  • a preferred ratio of the hydrofluoroolefin, preferably HFO-1234yf component in combination with a hydrochlorofluoroolefin (HCFO) preferably selected from HCFO-1223, HCFO-1233zd, HCFO-1233xf and mixtures thereof is more than about 5 wt % hydrofluoroolefin.
  • HCFO hydrochlorofluoroolefin
  • hydrofluoroolefin preferably HFO-1234yf in combination with a hydrochlorofluoroolefin (HCFO) preferably selected from HCFO-1223, HCFO-1233zd, HCFO-1233xf and mixtures thereof composition of the present invention
  • HCFO hydrochlorofluoroolefin
  • low or zero ozone depletion value materials including but not limited to: (a) hydrofluorocarbons including but not limited to difluoromethane (HFC32); 1,1,1-trifluoroethane (143a); 1,1,1,2,2-pentafluoroethane (HFC125); 1,1,2,2-tetrafluoroethane (HFC134); 1,1,1,2-tetrafluoroethane (HFC134a); 1,1-difluoroethane (HFC152a); 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea); 1,1,1,3,3-pentafluor
  • hydrofluoroolefins other than HFO-1234yf, including but not limited to tetrafluoropropenes such as HFO1234ze; trifluoropropenes such as HFO1243zf, all tetrafluorobutene isomers (HFO1354), all pentafluorobutene isomers (HFO1345), all hexafluorobutene isomers (HFO1336), all heptafluorobutene isomers (HFO1327), all heptafluoropentene isomers (HFO1447) all octafluoropentene isomers (HFO1438), all nonafluoropentene (HFO1429) (c) hydrocarbons including but not limited to, pentane isomers, butane isomers, (d) C1 to C5 alcohols, C1 to C4 aldehydes, C1 to C4 esters, C1 to C
  • the foamable compositions of the present invention generally includes one or more components capable of forming foam having a generally cellular structure and a blowing agent, typically in a combination, in accordance with the present invention.
  • the one or more components comprise a thermosetting composition capable of forming foam and/or foamable compositions.
  • thermosetting compositions include polyurethane and polyisocyanurate foam compositions, and also phenolic foam compositions.
  • one or more of the present compositions are included as or part of a blowing agent in a foamable composition, or as a part of a two or more part foamable composition, which preferably includes one or more of the components capable of reacting and/or foaming under the proper conditions to form a foam or cellular structure.
  • the invention also relates to foam, and preferably closed cell foam, prepared from a polymer foam formulation containing a blowing agent comprising the compositions of the invention.
  • foamable compositions comprising thermosetting foams, such as polyurethane and polyisocyanurate foams, preferably low-density foams, flexible or rigid.
  • blowing agent combination of the present invention does not generally affect the operability of the present invention.
  • the various components of the blowing agent combination, and even the components of the present composition not be mixed in advance of introduction to the foaming equipment, or even that the components are not added to the same location in the foaming equipment.
  • two or more components of the blowing agent combination are combined in advance and introduced together into the foamable composition, either directly or as part of premix that is then further added to other parts of the foamable composition.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A blowing agent for thermosetting foams is disclosed. The blowing agent is a hydrofluoroolefin (HCFO), preferably HFCO-1234yf in combination with a hydrochlorofluoroolefin (HCFO) preferably one selected from HCFO-1233zd, HCFO-1223, HCFO-1233xf and mixtures thereof. The blowing agent is effective as a blowing agent in the manufacture of thermosetting foams.

Description

  • This application is a divisional of U.S. patent application Ser. No. 12/532,202 filed Sep. 21, 2009, which is the national phase under 35 USC §371 of prior PCT International Application Number PCT/US2008/058607, filed Mar. 28, 2008, which designated the United States and which claims priority to U.S. provisional patent application Ser. No. 60/908,751, filed Mar. 29, 2007.
    • FIELD OF THE INVENTION
  • The present invention relates to blowing agents for thermosetting foams. More particularly, the present invention relates to the use of at least one hydrofluoroolefin such as HFO-1234yf in combination with at least one hydrochlorofluoroolefin (HCFO) such as HCFO-1223, HCFO-1233zd, HCFO-1233xf and mixtures thereof as a blowing agent in the manufacture of thermosetting foams.
    • BACKGROUND OF THE INVENTION
  • The Montreal Protocol for the protection of the ozone layer, signed in October 1987, mandated the phase out of the use of chlorofluorocarbons (CFCs). Materials more “friendly” to the ozone layer, such as hydrofluorocarbons (HFCs) eg HFC-134a replaced chlorofluorocarbons. The latter compounds have proven to be green house gases, causing global warming and were regulated by the Kyoto Protocol on Climate Change, signed in 1998. The emerging replacement materials, hydrofluoropropenes, were shown to be environmentally acceptable i.e. has zero ozone depletion potential (ODP) and acceptable low global warming potential (GWP).
  • Currently used blowing agents for thermoset foams include HFC-134a, HFC-245fa, HFC-365mfc that have relatively high global warming potential, and hydrocarbons such as pentane isomers flammable and have low energy efficiency. Therefore, new alternative blowing agents are being sought. Halogenated hydroolefinic materials such as hydrofluoropropenes and/or hydrochlorofluoropropenes have generated interest as replacements for HFCs. The inherent chemical instability of these materials in the lower atmosphere provides the low global warning potential and zero or near zero ozone depletion properties desired.
  • The object of the present invention is to provide novel compositions that can serve as blowing agents for thermosetting foams that provide unique characteristics to meet the demands of low or zero ozone depletion potential, lower global warming potential and exhibit low toxicity.
    • SUMMARY OF THE INVENTION
  • The present invention relates to the use of blowing agents with negligible (low or zero) ozone-depletion and low global warming potential based upon unsaturated halogenated hydroolefins. The blowing agents comprise at least one hydrofluoroolefin preferably (HFO) HFO-1234yf in a combination with at least one hydrochlorofluoroolefin (HCFO) such as HCFO-1223, HCFO-1233zd, HCFO-1233xf and mixtures thereof. HFO-1234yf is 2,3,3,3-tetrafluoropropene; HCFO 1223 is dichlorotrifluoropropene; HCFO-1233zd is 1-chloro-3,3,3-trifluoropropene; HCFO1233xf is 2-chloro-3,3,3-trifluoropropene. The composition can further comprise an additional hydrofluoroolefin (HFO), a hydrofluorocarbon, a hydrocarbon, an alcohol, an ester, an aldehyde, a ketone ether/diether, carbon dioxide and mixtures thereof.
  • Hydrofluoroolefin (HFO) materials have been proposed as blowing agents which exhibit a low global warming potential and a low ozone depletion value. The low global warming potential and a low ozone depletion value are a result of the atmospheric degradation of the hydrofluoroolefins.
  • The hydrofluoroolefin, preferably HFO-1234yf in combination with a hydrochlorofluoroolefin (HCFO) preferably selected from HCFO-1223, HCFO-1233zd, HCFO-1233xf and mixtures thereof combination can be used as a foaming agent for thermosetting foams by being mixed in a polyols mixture. The resulted products show superior quality including decreased density and improved k-factor. The foaming agent dissolves in thermosetting polymers, and provides a degree of plasticization sufficient to produce acceptable foams.
  • The preferred blowing agent composition, hydrofluoroolefin, preferably HFO-1234yf in combination with a hydrochlorofluoroolefin (HCFO) preferably selected from HCFO-1223, HCFO-1233zd, HCFO-1233xf and mixtures thereof of the present invention exhibits good solubility in polyol mixture used in producing polyurethane and polyisocyanurate foams. A preferred ratio of the hydrofluoroolefin, preferably HFO-1234yf component in combination with a hydrochlorofluoroolefin (HCFO) preferably selected from HCFO-1223, HCFO-1233zd, HCFO-1233xf and mixtures thereof is more than about 5 wt % hydrofluoroolefin.
  • The hydrofluoroolefin, preferably HFO-1234yf in combination with a hydrochlorofluoroolefin (HCFO) preferably selected from HCFO-1223, HCFO-1233zd, HCFO-1233xf and mixtures thereof composition of the present invention may be used in combination with low or zero ozone depletion value materials including but not limited to: (a) hydrofluorocarbons including but not limited to difluoromethane (HFC32); 1,1,1-trifluoroethane (143a); 1,1,1,2,2-pentafluoroethane (HFC125); 1,1,2,2-tetrafluoroethane (HFC134); 1,1,1,2-tetrafluoroethane (HFC134a); 1,1-difluoroethane (HFC152a); 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea); 1,1,1,3,3-pentafluoropropane (HFC245fa); 1,1,1,3,3-pentafluorobutane (HFC365mfc) and 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee). (b) additional hydrofluoroolefins, other than HFO-1234yf, including but not limited to tetrafluoropropenes such as HFO1234ze; trifluoropropenes such as HFO1243zf, all tetrafluorobutene isomers (HFO1354), all pentafluorobutene isomers (HFO1345), all hexafluorobutene isomers (HFO1336), all heptafluorobutene isomers (HFO1327), all heptafluoropentene isomers (HFO1447) all octafluoropentene isomers (HFO1438), all nonafluoropentene (HFO1429) (c) hydrocarbons including but not limited to, pentane isomers, butane isomers, (d) C1 to C5 alcohols, C1 to C4 aldehydes, C1 to C4 esters, C1 to C4 ketones, C1 to C4 ethers and diethers and carbon dioxide
  • The foamable compositions of the present invention generally includes one or more components capable of forming foam having a generally cellular structure and a blowing agent, typically in a combination, in accordance with the present invention. In certain embodiments, the one or more components comprise a thermosetting composition capable of forming foam and/or foamable compositions. Examples of thermosetting compositions include polyurethane and polyisocyanurate foam compositions, and also phenolic foam compositions. In such thermosetting foam embodiments, one or more of the present compositions are included as or part of a blowing agent in a foamable composition, or as a part of a two or more part foamable composition, which preferably includes one or more of the components capable of reacting and/or foaming under the proper conditions to form a foam or cellular structure.
  • The invention also relates to foam, and preferably closed cell foam, prepared from a polymer foam formulation containing a blowing agent comprising the compositions of the invention. In yet other embodiments, the invention provides foamable compositions comprising thermosetting foams, such as polyurethane and polyisocyanurate foams, preferably low-density foams, flexible or rigid.
  • It will be appreciated by those skilled in the art that the order and manner in which the blowing agent combination of the present invention is formed and/or added to the foamable composition does not generally affect the operability of the present invention. For example, in the case of polyurethane foams, it is possible that the various components of the blowing agent combination, and even the components of the present composition, not be mixed in advance of introduction to the foaming equipment, or even that the components are not added to the same location in the foaming equipment. Thus, in certain embodiments it may be desired to introduce one or more components of the blowing agent combination in a blender with the expectation that the components will come together in the foaming equipment and/or operate more effectively in this manner. Nevertheless, in certain embodiments, two or more components of the blowing agent combination are combined in advance and introduced together into the foamable composition, either directly or as part of premix that is then further added to other parts of the foamable composition.
  • Although the invention is illustrated and described herein with reference to specific embodiments, it is not intended that the appended claims be limited to the details shown. Rather, it is expected that various modifications may be made in these details by those skilled in the art, which modifications may still be within the spirit and scope of the claimed subject matter and it is intended that these claims be construed accordingly.

Claims (10)

1. A polymer blowing agent composition for thermosetting foams comprising (a) HFO-1234yf, (b) HCFO-1233zd, and (c) a component selected from the group consisting of a second hydrofluoroolefin (HFO), a hydrofluorocarbon, a hydrocarbon, an alcohol, an ester, an aldehyde, a ketone ether/diether, carbon dioxide and mixtures thereof, wherein said HFO-1234yf comprises about 5 wt % or more of said polymer blowing agent composition.
2. The polymer blowing agent composition of claim 1 wherein said second hydrofluoroolefin (HFO) is selected from the group consisting of tetrafluoropropenes; trifluoropropenes; tetrafluorobutene isomers; pentafluorobutene isomers; hexafluorobutene isomers; heptafluorobutene isomers; heptafluoropentene isomers; octafluoropentene isomers and nonafluoropentene isomers.
3. The polymer blowing agent composition of claim 1 wherein said second hydrofluoroolefin (HFO) is selected from the group consisting HFO-1234ze; HFO-1243zf; HFO-1354; HFO-1345; HFO-1336; HFO-1327; HFO-1447; HFO-1438 and HFO-1429.
4. The polymer blowing agent of claim 1 wherein said hydrofluorocarbon is selected from the group consisting of difluoromethane (HFC32); 1,1,1,2,2-pentafluoroethane (HFC125); 1,1,1-trifluoroethane (HFC143a); 1,1,2,2-tetrafluorothane (HFC134); 1,1,1,2-tetrafluoroethane (HFC134a); 1,1-difluoroethane (HFC152a); 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea); 1,1,1,3,3-pentafluoropropane (HFC245fa); 1,1,1,3,3-pentafluorobutane (HFC365mfc) and 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee).
5. A foam forming composition comprising a polyol mixture and the polymer blowing agent composition of claim 1.
6. A process of foaming a polyurethane foam comprising mixing polymer foam components with a foam blowing agent comprising (a) HFO-1234yf in combination with (b) at least one hydrochlorofluoroolefin (HCFO).
7. The process of claim 6 wherein said hydrochlorofluoroolefin is selected from the group consisting of HCFO-1233zd, HCFO-1223, HCFO-1233xf and mixtures and further wherein said HFO-1234yf comprises about 5 wt % or more of said polymer blowing agent composition.
8. The process of claim 6, wherein said foam blowing agent further comprises a hydrofluorocarbon.
9. The process of claim 8 wherein said hydrofluorocarbon is selected from the group consisting of difluoromethane (HFC32); 1,1,1,2,2-pentafluoroethane (HFC125); 1,1,1-trifluoroethane (HFC143a); 1,1,2,2-tetrafluorothane (HFC134); 1,1,1,2-tetrafluoroethane (HFC134a); 1,1-difluoroethane (HFC152a); 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea); 1,1,1,3,3-pentafluoropropane (HFC245fa); 1,1,1,3,3-pentafluorobutane (HFC365mfc) and 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee).
10. The process of claim 6, further comprising a second hydrofluoroolefin selected from the group consisting of HFO-1234ze, HFO-1243zf, HFO-1354, HFO-1345, HFO-1336, HFO-1327, HFO-1447, HFP-1438 and HFP-1429.
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Families Citing this family (81)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090253820A1 (en) * 2006-03-21 2009-10-08 Honeywell International Inc. Foaming agents and compositions containing fluorine sustituted olefins and methods of foaming
US9499729B2 (en) * 2006-06-26 2016-11-22 Honeywell International Inc. Compositions and methods containing fluorine substituted olefins
TW201815923A (en) † 2005-06-24 2018-05-01 美商哈尼威爾國際公司 Foaming agent and composition containing fluorine-substituted olefin, and foaming method
US9695267B2 (en) * 2009-08-11 2017-07-04 Honeywell International Inc. Foams and foamable compositions containing halogenated olefin blowing agents
CN101652411B (en) * 2007-03-29 2013-01-23 阿科玛股份有限公司 Blowing agent compositions of hydrofluoroolefins and hydrochlorofluoroolefins
AU2008279420A1 (en) * 2007-07-20 2009-01-29 E. I. Du Pont De Nemours And Company Compositions and use of trans-1,1,1,4,4,4-hexafluoro-2-butene foam-forming composition in the preparation of polyisocyanate-based foams
US8333901B2 (en) 2007-10-12 2012-12-18 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US8628681B2 (en) 2007-10-12 2014-01-14 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US8512591B2 (en) 2007-10-12 2013-08-20 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
GB2457345B (en) * 2007-10-12 2012-02-08 Ineos Fluor Holdings Ltd Heat transfer compositions
GB201002625D0 (en) 2010-02-16 2010-03-31 Ineos Fluor Holdings Ltd Heat transfer compositions
WO2009089400A1 (en) * 2008-01-11 2009-07-16 E. I. Du Pont De Nemours And Company Compositions and use of 2-chloro-3,3,3-trifluoropropene foam-forming composition in the preparation of polyisocyanate-based foams
EP2250144A4 (en) 2008-03-07 2014-06-04 Arkema Inc Stable formulated systems with chloro-3,3,3-trifluoropropene
US8877086B2 (en) * 2008-05-07 2014-11-04 E I Du Pont De Nemours And Company Compositions comprising 2,3-dichloro-1,1,1-trifluoropropane, 2-chloro-1,1,1-trifluoropropene, 2-chloro-1,1,1,2-tetrafluoropropane or 2,3,3,3-tetrafluoropropene
EP2313450A1 (en) * 2008-08-13 2011-04-27 E. I. du Pont de Nemours and Company Foam-forming compositions containing mixtures of 2-chloro-3,3,3-trifluoropropene and hydrocarbon and their uses in the preparation of polyisocyanate-based foams
US8163196B2 (en) * 2008-10-28 2012-04-24 Honeywell International Inc. Azeotrope-like compositions comprising 1-chloro-3,3,3-trifluoropropene
AU2009323869A1 (en) * 2008-12-02 2010-06-10 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
EP2391691A4 (en) * 2009-01-29 2013-09-18 Arkema Inc BLOOM COMPOSITIONS BASED ON TETRAFLUORPROPES
US20100216904A1 (en) * 2009-02-24 2010-08-26 E. I. Du Pont De Nemours And Company Foam-forming compositions containing mixtures of 2-chloro-3,3,3-trifluoropropene and at least one hydrofluoroolefin and their uses in the preparation of polyisocyanate-based foams
TW201103972A (en) 2009-04-01 2011-02-01 Solvay Fluor Gmbh Process for the manufacture of etched items
US8541478B2 (en) 2009-05-21 2013-09-24 Huntsman International Llc Rigid polyurethane foam and system and method for making the same
AR078600A1 (en) * 2009-06-02 2011-11-23 Du Pont AZEOTROPIC AND QUASI-AZEOTROPIC COMPOSITIONS OF Z-1,1,1,4,4,4-HEXAFLUORO-2- BUTENO AND PROCESS TO PREPARE A THERMOPLASTIC FOAM
US20120145955A1 (en) * 2009-07-27 2012-06-14 Arkema Inc. COMPOSITION OF HCFO-1233zd AND POLYOL BLENDS FOR USE IN POLYURETHANE FOAM
DE102009028061A1 (en) 2009-07-29 2011-02-10 Evonik Goldschmidt Gmbh Process for the production of polyurethane foam
EP4219645A1 (en) * 2009-09-09 2023-08-02 Honeywell International, Inc. Monochlorotrifluoropropene compounds and compositions and methods using same
BR112012009517C8 (en) * 2009-10-23 2020-04-14 Arkema Inc polyurethane foaming process, foamed thermosetting composition and use of polymeric blowing agent composition
US8846754B2 (en) * 2009-12-16 2014-09-30 Honeywell International Inc. Azeotrope-like compositions of cis-1,1,1,4,4,4-hexafluoro-2-butene
ES2762350T3 (en) 2009-12-22 2020-05-22 Chemours Co Fc Llc Compositions comprising 2,3,3,3-tetrafluoropropene and 2,3-dichloro-3,3-difluoropropene
GB201002622D0 (en) 2010-02-16 2010-03-31 Ineos Fluor Holdings Ltd Heat transfer compositions
US8821749B2 (en) * 2010-04-26 2014-09-02 E I Du Pont De Nemours And Company Azeotrope-like compositions of E-1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoropropene
GB2480513B (en) 2010-05-20 2013-01-02 Mexichem Amanco Holding Sa Heat transfer compositions
WO2011144908A2 (en) 2010-05-20 2011-11-24 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
GB2481443B (en) 2010-06-25 2012-10-17 Mexichem Amanco Holding Sa Heat transfer compositions
US20120043492A1 (en) * 2010-08-17 2012-02-23 Honeywell International Inc. Compositions Containing 1-Chloro-3,3,3 Trifluoropropene And 1-Fluoro-1,1 Dichloroethane
US20120046372A1 (en) * 2010-08-18 2012-02-23 Honeywell International Inc. Blowing agents, foamable compositions and foams
US9145480B2 (en) * 2010-10-28 2015-09-29 Honeywell International Inc. Mixtures containing 1,1,1,3,3,3-hexafluorobutene and 1-chloro-3,3,3-trifluoropropene
US8680168B2 (en) 2010-11-17 2014-03-25 Fomo Products, Inc. Method for filling wall cavities with expanding foam insulation
US8734671B2 (en) * 2010-11-19 2014-05-27 Honeywell International Inc. Azeotrope-like compositions comprising 1-chloro-3,3,3-trifluoropropene
EP2643419B1 (en) * 2010-11-25 2019-05-08 Arkema France Compositions of chloro-trifluoropropene and hexafluorobutene
FR2968310B1 (en) * 2010-12-03 2012-12-07 Arkema France COMPOSITIONS BASED ON 1,1,1,4,4,4-HEXAFLUOROBUT-2-ENE AND 3,3,4,4,4-PENTAFLUOROBUT-1-ENE
US20140364528A1 (en) 2010-12-21 2014-12-11 Dow Global Technologies Llc Polyol formulations for improved cold temperature skin cure of polyurethane rigid foams
US9724684B2 (en) * 2011-02-21 2017-08-08 The Chemours Company Fc, Llc Selective catalytical dehydrochlorination of hydrochlorofluorocarbons
FR2977256B1 (en) * 2011-07-01 2013-06-21 Arkema France COMPOSITIONS OF 2,4,4,4-TETRAFLUOROBUT-1-ENE AND CIS-1,1,1,4,4,4-HEXAFLUOROBUT-2-ENE
BR112014002096A2 (en) * 2011-07-28 2017-06-13 Honeywell Int Inc method of forming a building envelope, method of applying a polyurethane or polyisocyanurate foam panel or board to a building envelope, and residential home, office building, office building, or craft
US9896558B2 (en) 2011-08-01 2018-02-20 Basf Se HFO/water-blown rigid foam systems
CN103717656B (en) 2011-08-01 2016-03-23 巴斯夫欧洲公司 HFO/water-blown rigid foam system
MX2014004563A (en) 2011-10-14 2014-08-01 Dow Global Technologies Llc Hybrid polyester-polyether polyols for improved demold expansion in polyurethane rigid foams.
CN103890065B (en) 2011-10-20 2016-02-03 纳幕尔杜邦公司 Azeotrope-like compositions of chloro-2,3,3, the 3-tetrafluoeopropenes of E-1-and uses thereof
JP2015500362A (en) * 2011-12-09 2015-01-05 ハネウェル・インターナショナル・インコーポレーテッド Articles made from foam and foam comprising HCFO or HFO blowing agent
JP2015507039A (en) * 2011-12-22 2015-03-05 ハネウェル・インターナショナル・インコーポレーテッド An azeotrope-like composition comprising cis-1-chloro-3,3,3-trifluoropropene
US8921621B2 (en) 2012-02-15 2014-12-30 Honeywell International Inc. Process for the production of HCFC-1233zd
US9000239B2 (en) * 2012-05-15 2015-04-07 Honeywell International Inc. Methods for producing 1-chloro-3,3,3-trifluoropropene from 2-chloro-3,3,3-trifluoropropene
MX373430B (en) 2012-05-25 2020-05-20 Dow Global Technologies Llc PRODUCTION OF POLYISOCYANURATE FOAM PANELS.
CN104781315B (en) * 2012-09-07 2019-03-08 巴斯夫欧洲公司 Shrinkage-reduced rigid polyurethane foam
CN102850571A (en) * 2012-09-28 2013-01-02 关志强 Foaming agent for insulating polyurethane plastics
FR3000094B1 (en) * 2012-12-26 2019-10-18 Arkema France COMPOSITION COMPRISING 1,1-DIFLUOROETHANE AND 3,3,3-TRIFLUOROPROPENE
CN104046331A (en) * 2013-03-14 2014-09-17 霍尼韦尔国际公司 Low GWP fluids for high temperature heat pump applications
CA2907180C (en) 2013-03-15 2021-08-10 Owens Corning Intellectual Capital, Llc Processing aids for use in manufacturing extruded polystyrene foams using low global warming potential blowing agents
US20150210818A1 (en) * 2014-01-27 2015-07-30 E I Du Pont De Nemours And Company Cryogenic insulation foam
CN103881131A (en) * 2014-03-17 2014-06-25 浙江衢化氟化学有限公司 Environment-friendly foaming agent composition
WO2015168486A1 (en) * 2014-04-30 2015-11-05 Honeywell International Inc. Flexible, open-cell thermoset foams and blowing agents and methods for making same
US10330364B2 (en) 2014-06-26 2019-06-25 Hudson Technologies, Inc. System and method for retrofitting a refrigeration system from HCFC to HFC refrigerant
CN104119490A (en) * 2014-07-10 2014-10-29 合肥美的电冰箱有限公司 A composition, a foam material prepared from the composition, a preparing method of the foam material and applications of the foam material
MX2017000515A (en) * 2014-07-16 2017-08-18 Owens Corning Intellectual Capital Llc Non-voc processing aids for use in manufacturing foams using low global warming potential blowing agents.
JP6626674B2 (en) * 2014-10-08 2019-12-25 積水ソフランウイズ株式会社 Polyol composition for rigid polyurethane foam, and method for producing rigid polyurethane foam
EP3275927B1 (en) * 2015-03-24 2021-07-28 Sekisui Chemical Co., Ltd. Phenolic resin foam and method for producing phenolic resin foam
AU2016237952B2 (en) * 2015-03-24 2018-08-09 Asahi Kasei Construction Materials Corporation Phenol resin foam and method for producing same
KR102699589B1 (en) 2015-05-21 2024-08-28 더 케무어스 컴퍼니 에프씨, 엘엘씨 Hydrofluorination of 1233xf to 244bb by SbF5
JP6274363B2 (en) * 2015-07-27 2018-02-07 旭硝子株式会社 Solvent composition, cleaning method, coating film forming method, heat transfer medium and thermal cycle system
CN105885080A (en) * 2016-05-05 2016-08-24 巨化集团技术中心 Foamer composition and preparation method thereof
CH712779A1 (en) * 2016-07-20 2018-01-31 Brugg Rohr Ag Holding Barrier layers.
US10131758B2 (en) 2016-07-25 2018-11-20 Accella Polyurethane Systems, Llc Polyurethane foam-forming compositions, methods of making low density foams using such compositions, and foams formed therefrom
CN106750488B (en) * 2016-12-26 2019-05-17 浙江衢化氟化学有限公司 A kind of low-carbon environment-friendly foaming agent
CN108727551A (en) * 2017-04-19 2018-11-02 科思创德国股份有限公司 A kind of hard polyurethane foams and the preparation method and application thereof
CN108102333A (en) * 2017-12-27 2018-06-01 上海东大聚氨酯有限公司 A kind of ultralow temperature incubator combined polyether, polyurethane raw material composition, polyurethane foam and preparation method thereof
CN112236510B (en) * 2018-07-27 2022-04-22 中央硝子株式会社 Solvent composition
CN110105520B (en) * 2019-05-05 2021-09-21 深圳市盈石科技有限公司 Heat-insulating rigid polyurethane foam and preparation method thereof
MX2022009160A (en) 2020-02-04 2022-08-16 Chemours Co Fc Llc NUCLING AGENTS FOR POLYISOCYANURATE (PIR) FOAMS.
WO2022009801A1 (en) * 2020-07-08 2022-01-13 Ａｇｃ株式会社 Composition and use thereof
CN114149790B (en) * 2021-11-10 2023-09-05 浙江巨化新材料研究院有限公司 Azeotropic or azeotrope-like compositions and methods of making same
CN117940474A (en) * 2022-05-20 2024-04-26 海信容声(广东)冰箱有限公司 Polyurethane foam material and preparation method thereof, refrigerator and freezer

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2039008A (en) 1932-07-28 1936-04-28 Burgess Lab Inc C F Method of making a material for absorbing sound
JPH02221388A (en) 1989-02-23 1990-09-04 Asahi Glass Co Ltd Degreasing detergent
JP2751428B2 (en) * 1989-06-30 1998-05-18 旭硝子株式会社 3,3-dichloro-1,1,1,2,2-pentafluoropropane-based composition
JPH05179042A (en) * 1991-11-18 1993-07-20 Daikin Ind Ltd Blowing agent comprising fluoropropene and production of plastic foam
US5710352A (en) 1996-09-19 1998-01-20 Alliedsignal Inc. Vapor phase process for making 1,1,1,3,3-pentafluoropropane and 1-chloro-3,3,3-trifluoropropene
DE69807962T2 (en) 1997-03-11 2003-01-30 Central Glass Co., Ltd. Process for the purification of crude 1,1,1,3,3-pentafluoropropane
US6013846A (en) * 1998-03-05 2000-01-11 Elf Atochem North America, Inc. Azeotrope of HF and 1233zd
US20050096246A1 (en) * 2003-11-04 2005-05-05 Johnson Robert C. Solvent compositions containing chlorofluoroolefins
US7279451B2 (en) * 2002-10-25 2007-10-09 Honeywell International Inc. Compositions containing fluorine substituted olefins
US9796848B2 (en) * 2002-10-25 2017-10-24 Honeywell International Inc. Foaming agents and compositions containing fluorine substituted olefins and methods of foaming
CA2503421C (en) * 2002-10-25 2015-01-06 Rajiv R. Singh Compositions containing fluorine substituted olefins
US20090253820A1 (en) 2006-03-21 2009-10-08 Honeywell International Inc. Foaming agents and compositions containing fluorine sustituted olefins and methods of foaming
US9499729B2 (en) 2006-06-26 2016-11-22 Honeywell International Inc. Compositions and methods containing fluorine substituted olefins
US7098176B2 (en) * 2004-04-16 2006-08-29 Honeywell International Inc. Azeotrope-like compositions of tetrafluoropropene and pentafluoropropene
MX2007007457A (en) * 2004-12-21 2007-08-20 Honeywell Int Inc Stabilized iodocarbon compositions.
US20060243944A1 (en) 2005-03-04 2006-11-02 Minor Barbara H Compositions comprising a fluoroolefin
US20060243945A1 (en) * 2005-03-04 2006-11-02 Minor Barbara H Compositions comprising a fluoroolefin
TWI645031B (en) 2005-06-24 2018-12-21 哈尼威爾國際公司 Compositions containing fluorine substituted olefins amd uses thereof
TW201815923A (en) 2005-06-24 2018-05-01 美商哈尼威爾國際公司 Foaming agent and composition containing fluorine-substituted olefin, and foaming method
CA2681832C (en) 2007-03-29 2016-01-26 Arkema Inc. Blowing agent composition of hydrochlorofluoroolefin
CN100488925C (en) 2007-04-11 2009-05-20 西安近代化学研究所 Method for producing 1,1,1,3-tetrafluoroethylene

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